Methods of using manganese chloride for improving the wetting of particulates

ABSTRACT

New and improved compositions comprising particulates and an effective amount of manganese chloride to reduce significantly the wetting time and/or the dispersion time of said particulates relative to said time(s) in the absence of said salt(s) have been discovered. Methods for reducing the wetting time of particulates in liquid have also been discovered.

This is a divisional of application U.S. Ser. No. 08/420,393, filed Apr.12, 1995, now U.S. Pat. No. 5,516,748, which is continuation of U.S.Ser. No. 08/033,997, filed Mar. 19, 1993, now abandoned; which is acontinuation-in-part of U.S. Ser. No. 07/877,332, filed May 1, 1992, nowabandoned.

BACKGROUND

Compositions containing particulates are often admixed with liquidcompositions for application purposes. This broad operation includesmixing of powders in the household to making medical solutions to otherapplications such as on-site preparation of solutions in industrial oragricultural applications. Examples, without limitations, range frommixing flour with water in baking to making herbicidal or fungicidalagricultural compositions for field spraying or other distributingmethods. One parameter of such operations is the time that it takes forthe particulates to become wetted (i.e. "wetting time" or "wet-outtime") to permit dispersion or dissolution of the particulates in aliquid application medium. "Wetting time" or "wet-out time" can bedesignated as the time for a known weight of solids poured on top ofwater in a container to completely submerge below the surface of thewater. The wetting time can have a major impact on the time ofoperations, delays associate therewith, the degree of completion ofdissolution or dispersion and the effectiveness of the appliedcomposition as a result of incomplete dissolution or dispersion.

There continues to be a need for new and/or improved compositions ormethods to improve the wetting time of particulates.

SUMMARY OF THE INVENTION

New and improved compositions comprising particulates and an effectiveamount of one or more salt(s) to increase the penetration rate of liquidinto the particulates relative to the rate of penetration in the absenceof said salt(s) have been discovered. Preferably, the increase in therate of penetration results in reducing the wetting time and/or thedispersion time of said particulates in liquids. Methods for reducingthe wetting time of particulates in liquids have also been discovered.

EMBODIMENTS OF THE INVENTION

An embodiment of the present invention is a composition comprisingparticulates and an effective amount of one or more ammonium salt(s),boron salt(s), and/or effective metal salt(s) to increase thepenetration rate of liquid into the particulates relative to the rate ofpenetration in the absence of said salt(s).

In a preferred embodiment the present invention is a compositioncomprising particulates and an effective amount of one or more ammoniumsalt(s), boron salt(s), and/or effective metal salt(s) to reducesignificantly the wetting time and/or the dispersion time of saidparticulates in liquid relative to said time(s) in the absence of saidsalt(s).

The particulates and liquid in the invention can be any usablecombination of particulates and liquid for an intended utility. Forexample, the particulates could be commercial foodstuff, e.g. powderedmilk, flour etc., and the liquid can be water or water-containingsolutions (e.g. milk). Other combinations include agriculturalutilities, such as in-field formulations of agrochemicals, e.g.herbicides etc., and water. It is not intended that the presentinvention is limited to water as the liquid by these examples.

The effective salts usable in the invention preferably comprise ammoniumor boron, or one or more metals selected from zinc, manganese, copper,iron, cobalt, aluminum, magnesium, calcium, strontium, sodium, barium,tin, lead, silver, nickel, and potassium. Such ammonium, boron or metalmoieties are alternatively referred to as the cation of the salt. Theanionic portion of the salt is preferably a moiety such that the one ormore salt(s) has an anion portion which is SO₄ ⁻², Cl⁻¹, Br⁻¹, I⁻¹, C₂H₃ O₂ ⁻¹, CO₃ ⁻², NO₃ ⁻¹, OH⁻¹, S⁻², PO₄ ⁻³, AlO₂ ⁻¹, AsO₃ ⁻³, HAsO ₃⁻², H₂ AsO₃ ⁻¹, AsO₄ ⁻³, HAsO₄ ⁻², H₂ AsO₄ ⁻¹, B₄ O₇ ⁻², CN⁻¹, PO₃ ⁻³,HPO₃ ⁻², H ₂ PO₃ ⁻¹, HPO₄ ⁻², H₂ PO₄ ⁻¹, P₂ O₇ ⁻⁴, S₂ O₆ ⁻², CHO₂ ⁻¹,SO₃ ⁻² or a mixture thereof.

The amount of salt used is that amount which is effective to increasethe penetration rate of liquid into the particulate, preferably asignificant amount of increase. For example, the increase in penetrationrate is such that the wet-out time is about thirty percent less, morepreferably about fifty percent less, even more preferably aboutseventy-five percent less, than that without the effective salts. Theweight amount of the salt can range preferably from about 0.1 to about50 weight percent, more preferably from about 0.1 to about 10 weightpercent, even more preferably from about 0.1 to about 6 weight percent,of the total composition weight. In one preferred embodied compositionthe amount of effective salt in the composition is in a weight percentof from about 0.1 percent to about 6 percent and the wet-out time of thecomposition is less than about fifty percent of the wet-out time of acomparable composition having an absence of said salt.

The particular form or nature of the salt can vary and still provide thebenefits of the present invention. For instance, the one or more salt(s)can comprise a multiple salt complex. That is, it can be a complex oftwo or more different salts. For example, a multiple salt complex can berepresented by the formula 2NaCl.CaCl₂ or K₂ CO₃.Na₂ CO₃. Embodiedmultiple salt complexes can be hydrated, such as ZnCl₂.3ZnO.5H₂ O forexample.

Embodiment of the invention can comprise other forms of salt. Forinstance, the one or more salt(s) can comprise a hydrated salt. Forexample, the hydrated salt can be CuSO₄.H₂ O. The ratio of saltmolecules to water molecules need not be one to one.

The salt need not consist of only one cation in the salt compound.Accordingly, embodied compositions can comprise a multiple cation salt.One example of a multiple salt is K₂ Zn(SO₄)₂. Similarly, the anionicportion can have multiple anions.

One embodiment of the present invention is wherein the one or moresalt(s) comprise a melted salt. A mixture of salts can be meltedtogether for the melted salt. Examples are 2NaCl.CaCl₂, Na₂ SO₄.MgSO₄,and 2NaCl.SrCl₂.

Without limiting the scope of the present invention, the following saltsare representative of salts useable:

    __________________________________________________________________________    Zn(C.sub.2 H.sub.3 O.sub.2).sub.2.H.sub.2 O                                              Zn(C.sub.2 H.sub.3 O.sub.2).sub.2.2H.sub.2 O                                            Zn(C.sub.2 H.sub.3 O).sub.2                                                            CuCl.sub.2                                      CuSO.sub.4 Cu(NO.sub.3).sub.2                                                                      MnCl.sub.2.4H.sub.2 O                                                                  MnCl.sub.2                                      MnCl.sub.2.2H.sub.2 O                                                                    ZnSO.sub.4                                                                              ZnSO.sub.4.H.sub.2 O                                                                   MnSO.sub.4                                      CuCl.sub.2.2H.sub.2 O                                                                    CuSO.sub.4.H.sub.2 O                                                                    ZnBr.sub.2                                                                             Znl.sub.2                                       MnSO.sub.4.H.sub.2 O                                                                     Mn(NO.sub.3).sub.2                                                                      Mn(CHO.sub.2).sub.2                                                                    FeCl.sub.2                                      Mn(C.sub.2 H.sub.3 O.sub.2).sub.2                                                        FeCl.sub.3                                                                              FeCl.sub.2.2H.sub.2 O                                                                  FeCl.sub.2.4H.sub.2 O                           FeCl.sub.3.2.5H.sub.2 O                                                                  FeCl.sub.3.6H.sub.2 O                                                                   FeSO.sub.4                                                                             FeSO.sub.4.H.sub.2 O                            FeSO.sub.4.4H.sub.2 O                                                                    CoCl.sub.2                                                                              CoBr.sub.2                                                                             BBr.sub.3                                       CoCl.sub.2.2H.sub.2 O                                                                    AlCl.sub.3                                                                              AlCl.sub.3.6H.sub.2 O                                                                  AlBr.sub.3                                      All.sub.3  Al.sub.2 S.sub.3                                                                        AlCl.sub.3.SO.sub.2                                                                    AlCl.sub.3.5SO.sub.2                            AlCl.sub.3.5H.sub.2 S                                                                    Al.sub.2 (SO.sub.4).sub.3.6H.sub.2 O                                                    Al.sub.2 (SO.sub.4).sub.3.18H.sub.2 O                                                  AlCl.sub.3.NH.sub.3                             AlCl.sub.3.3NH.sub.3                                                                     AlCl.sub.3.NH.sub.4 Cl                                                                  AlCl.sub.3.5NH.sub.3                                                                   AlCl.sub.3.6NH.sub.3                            AlCl.sub.3.9NH.sub.3                                                                     AlCl.sub.3.3/4ZnCl.sub.2                                                                AlCl.sub.3.AgCl                                                                        MgCl.sub.2                                      MgCl.sub.2.2H.sub.2 O                                                                    MgCl.sub.2.4H.sub.2 O                                                                   MgCl.sub.2.6H.sub.2 O                                                                  MgBr.sub.2                                      MgSO.sub.4 MgSO.sub.4.H.sub.2 O                                                                    MgSO.sub.4.2H.sub.2 O                                                                  CaCl.sub.2                                      CaCl.sub.2.H.sub.2 O                                                                     CaCl.sub.2.2H.sub.2 O                                                                   Ca(NO.sub.3).sub.2                                                                     CaBr.sub.2                                      Ca(C.sub.2 H.sub.3 O.sub.2).sub.2.H.sub.2 O                                              Cal.sub.2 CaSO.sub.4                                                                             Mgl.sub.2                                       MgSO.sub.4.4H.sub.2 O                                                                    SrO       SrCl.sub.2                                                                             SrBr.sub.2                                      SrBr.sub.2.H.sub.2 O                                                                     SrBr.sub.2.2H.sub.2 O                                                                   Na.sub.2 O                                                                             NaOH                                            NaOH.1/2H.sub.2 O                                                                        NaOH.H.sub.2 O                                                                          Na.sub.2 S                                                                             NaHS.sub.2                                      Na.sub.2 Se                                                                              NaPO.sub.3                                                                              Na.sub.2 P.sub.2 Cl.sub.7                                                              Na.sub.2 HPO.sub.3                              Na.sub.2 HPO.sub.4                                                                       Na.sub.3 HP.sub.2 O.sub.7                                                               Na.sub.2 CO.sub.3                                                                      NaCl.AlCl.sub.3                                 3NaCl.2AlCl.sub.3                                                                        KOH       K.sub.2 CO.sub.3.Na.sub.2 CO.sub.3                                                     ZnCl.sub.2                                      K.sub.2 CO.sub.3.2NaCO.sub.3                                                             K.sub.2 CO.sub.3.3Na.sub.2 CO.sub.3                                                     K.sub.2 CO.sub.3.4Na.sub.2 CO.sub.3                                                    K.sub.2 S                                       2K.sub.2 CO.sub.3.Na.sub.2 CO.sub.3                                                      3K.sub.2 CO.sub.3.Na.sub.2 CO.sub.3                                                     K.sub.2 CO.sub.3.1/2H.sub.2 O                                                          KC.sub.2 H.sub.3 O.sub.2                        K.sub.2 Zn(SO.sub.4).sub.2                                                               KCl.AlCl.sub.3                                                                          2KCN.Zn(CN).sub.2                                                                      KCl.MgCl.sub.2                                  K.sub.2 SO.sub.4.CuSO.sub.4                                                              3KCl.2AlCl.sub.3                                                                        3KCl.AlCl.sub.3                                                                        2KCl.MgCl.sub.2                                 Mn(C.sub.2 H.sub.3 O.sub.2).sub.2.4H.sub.2 O                                             4KCl.MgCl.sub.2                                                                         K.sub.2 Mg(SO.sub.4).sub.2                                                             2KCl.CaCl.sub.2                                 Melted salt mixtures:                                                                    Na.sub.2 SO.sub.4.MgSO.sub.4                                                            2NaCl.CaCl.sub.2                                                                       2NaCl.SrCl.sub.2                                __________________________________________________________________________

Other embodiments include compositions wherein the solid particulatescomprise one or more dithiocarbamate compound(s). In one embodimentthere is preferred one or more dithiocarbamate compound(s) which areselected from ethylenebisdithiocarbamate metal salts,dimethyldithiocarbamate metal salts, propylenebisdithiocarbamate metalsalts, and/or metiram-complex. Metiram-complex can be named as tris[ammine-[ethylen bis (dithiocarbamato)] zinc (II)][tetrahydro-1,2,4,7-dithiadiazocine-3,8-dithione] polymer. In anotherembodiment, thiram [e.g. bis (dimethylthio-carbamoyl) disulfide can beused in place of the dithiocarbamate compound. A preferredethylenebisdithiocarbamate metal salt comprises zinc chloride. Alsopreferred are compositions wherein the solid particulates compriseN-(3,4-dichlorophenyl)propionamide (propanil). Such compositions canhave applications in agricultural operations.

Embodied compositions can additionally comprise a surface active agentin an amount up to about twenty (20) weight percent of the totalcomposition weight, preferably from about 0.1 percent to about 15percent, more preferably from about 1 percent to about 10 percent.Preferred surface active agents are, but are not limited to, a groupconsisting of WAFEX™ dispersant; IGEPAL™ CA 720 surfactant, Igepal CO630 surfactant, Igepal DM 970 surfactant, Borresperse™ NA ligosulfonate,Aerosol™ OT-70PG surfactant, and Surfynol™ 104 S surfactant.

Also embodied are methods for wetting solid particulates in a liquidcomprising admixing the solid particulates with one or more embodiedsalt(s) prior to, comtemporaneous with, or after adding the solidparticulates to a liquid for wetting, dissolution or dispersion. Suchmethods can include simple admixing steps or milling of the solidparticulates with the one or more embodied salt(s) so as to adfix oradhere the salt to the surface of the solid particulate.

The following examples are intended to illustrate but not limit thescope of the embodied invention.

EXPERIMENT 1

A comparison of wetting time was made between regular baking flourwithout zinc chloride and with zinc chloride. The samples of flour withzinc chloride were prepared by first admixing the flour and zincchloride powder (98%, A.C.S. reagent, Aldrich Chemical Company, Inc.)before addition to 100 ml of tap water for timing to wet-out condition.No stirring was performed after the addition of sample to the water. Thefollowing results were obtained:

    ______________________________________                                        Sample                                                                              Flour Weight  ZnCl.sub.2 Weight                                                                        Wet-Out Time                                   No.   (grams)       (grams)    (seconds)                                      ______________________________________                                        1     5.00          0.30       302                                            2     5.00          0.30       269                                            3     5.00          0.00       815                                            4     5.00          0.00       790                                            ______________________________________                                    

EXPERIMENT 2

A mancozeb powder was produced by spray-drying a slurry composed of thefollowing components:

    ______________________________________                                        Component            Weight Percent                                           ______________________________________                                        Maneb Wet-cake*      65.9                                                     ZnSO.sub.4.7H.sub.2 O                                                                              3.8                                                      Hexamethylenetetramine Stabilizer                                                                  1.1                                                      Reax ™ 100M Dispersant                                                                          3.3                                                      Water                25.9                                                     ______________________________________                                         *The wet cake prior to admixing is about 55% manganese                        ethylenebisdithiocarbamate.                                              

The spray-dried mancozeb powder was separated into two samples, onesample being dry mixed with zinc chloride in a weight ratio of zincchloride:mancozeb=2:100. Using procedures similar to Experiment 1, thefollowing results were observed:

    ______________________________________                                        Sample        Wet-out time (Minutes)                                          ______________________________________                                        without ZnCl.sub.2                                                                          12.0                                                            with ZnCl.sub.2                                                                             3.5                                                             ______________________________________                                    

    ______________________________________                                        Sample                                                                              ZnSO.sub.4.      Surface Active  Wet-Out                                No    7H.sub.2 O                                                                             ZnCl.sub.2                                                                            Agent*    Water Time(secs)                             ______________________________________                                        5     3.8      0.0     2.0.sup.b 26.7  51                                                            0.5.sup.c(2)                                           6     1.9      0.9     2.0.sup.b 28.2  60                                     7.sup.a                                                                             0.0      1.8     3.3.sup.d 27.85 55                                     8.sup.a                                                                             0.0      1.8     2.9.sup.d 26.62 28                                                            0.63.sup.e                                             9     0.0      1.8     2.9.sup.d 27.3  26                                                            1.sup.f                                                10    0.0      1.8     2.0.sup.b 29.2  16                                     ______________________________________                                         *Agents                                                                       .sup.a 0.05 weight percent Antifoam ™ C antifoaming agent [Corning]        added to these samples                                                        .sup.b Wafex ™ dispersant                                                  .sup.c(1) Igepal ™ CA 720, .sup.(2) Igepal CO 630, and .sup.(3) Igepal     DM 970 surfactants [Rhone Poulenc Company]-                                   .sup.d Borresperse ™ NA ligosulfonate [LignoTech Inc.]-                    .sup.e Aerosol ™ OT70PG surfactant [American Cyanamid]-                    .sup.f Surfynol ™ 104 S surfactant [Air Products & Chemicals Company].

EXPERIMENT 3

Samples of mancozeb powders which were spray-dried to a moisture contentof about 6 to about 9 percent water by weight were produced fromslurries comprising admixed 65.9 weight percent maneb wet-cake and 1.1weight percent hexamethylenetetramine stabilizer as well as thefollowing components in the reported weight percentages. The respectivereported wet-out times were observed. Suspensibility of each sample wasdetermined using the modified WHO method of admixing 2 grams of samplein 250 grams of water in a 250 milliliter cylinder, inverting thirtytimes and, after thirty minutes, collecting the bottom ten percent,which is then dried and weighed relative to the original 2 grams. Thesuspensibility for the samples ranged from about 60 to about 80 percent.

    ______________________________________                                        Sample                                                                              ZnSO.sub.4.      Surface Active  Wet-Out                                No    7H.sub.2 O                                                                             ZnCl.sub.2                                                                            Agent*    Water Time(secs)                             ______________________________________                                        1.sup.a                                                                             3.8      0.0     3.3.sup.d 27.85 779                                    2     3.8      0.0     2.0.sup.b 26.2  280                                    3     3.8      0.0     2.0.sup.b 26.7  80                                                            0.5.sup.c(3)                                           4     3.8      0.0     2.0.sup.b 26.7  73                                                            0.5.sup.c(1)                                           ______________________________________                                    

What is claimed is:
 1. A method for wetting particulates comprising:admixing a particulate material, wherein the particulate material is anagricultural chemical, with an effective amount of manganese chloridesuch that the particulate material is wetted, dissolved or dispersed inless than 50% of the time needed to wet, dissolve or disperse theparticulate material in the absence of manganese chloride.
 2. The methodof claim 1 wherein the amount of manganese chloride is from about 0.1 toabout 10% of the total weight of the particulate and manganese chloridemixture.
 3. The method of claim 1 wherein the particulate material isselected from the group consisting of propanil, thiram, anddithiocarbamate compounds.